Trinuclear merocyanine dyes containing a chain alkoxyl group



a chain substituent.

United States Patent TRINUCLEAR MEROCYANINE DYES CONTAIN- IN G A CHAIN ALKOXYL GROUP Edward B. Knott, Harrow, England, assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 20, 1953, Serial No. 343,809

11 Claims. (Cl. 260-2401) This invention relates to merocyanine dyes containing More particularly, this invention relates to complex merocyanine dyes containing an alkoxyl substituent on the intercyclic chain connecting two of the heterocyclic nuclei.

Certain merocarbocyanine dyes containing an alkoxyl substituent on the chain have been previously described. See, for example, Brooker and White U. S. Patents 2,478,366, issued August 9, 1949, and 2,494,031, issued January 10, 1950. However, complex merocyanine dyes containing an alkoxyl substituent have not been previously described. 7

I have now found a new class of complex merocyanine dyes containing an alkoxyl group attached to one of the carbon atoms of the iutercyclic chain.

It is, accordingly, an object of my invention to provide new complex merocyanine dyes. Still another object is to provide a method for making these new dyes. Another object is to provide photographic silver halide emulsions sensitized with my new dyes. Other objects will become apparent from a consideration of the following description and examples.

The new complex merocyanine dyes of my invention can advantageously be represented by the following general formula:

I o v 1|}--J OR:

wherein R and R3, each represents an alkyl group, such as methyl, ethyl, n-propyl, etc. (e. g. an alkyl group of the formula CnHzn+1 wherein n is a positive integer of from 1 to 3), R1 represents a memberselected from the group consisting of a hydrogen atom and an alkyl group, such as methyl, ethyl, n-propyl, etc. (e. g. an alkyl group of the formula CnH2n 1 wherein n represents a positive integer of from 1 to 3), R2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group, such as methyl, ethyl, n-propyl, etc. (e. g. an alkyl group of the formula CnH2n 1 wherein n is a positive integer of from 1 to 3), an aryl group, such as phenyl, m-, and p-tolyl, etc. (e. g. a monocyclic aryl group) and an alkoxyl group, such as methoxyl, ethoxyl, etc., I and 11 together represent the non-metallic atoms necessary to complete a thiazolidone nucleus, i. e. a 4 thiazolidone nucleus or a S-thiazolidone nucleus (i. e. I and J1 are different from one another and represent a sulfur atom or a l TRl group wherein R6 represents an alkyl group, such as methyl, ethyl, n-propyl, allyl, carboxymethyl, carbo-' methoxymethyl, carbethoxymethyl, etc., or an arylgroup, such as phenyl, 0-, m-, and p-tolyl, etc.), m and 22 each represents a positive integral of from 1' to 2, Z represents the non-metallic atoms necessary to complete a 2,728,766 Patented Dec. 27, 1955 2, in the heterocyclic ring, such as those selected from the group consisting of those of the thiazole series (e. g. thiazole, 4-methylthiazole, 4-phenylthiazole, S-methyl thiazole, 5 phenylthiazole, 4,5 dimethylthiazole, 4,5- diphenylthiazole, 4 (2 thienyl)thiazole, etc.), those of the benzothiazole series (e. g. benzothiazole, 4-chlorobenzothiazole, 5 chlorobenzothiazole, 6 chlorobenzothiazole, 7 chlorobenzothiazole, 4 methylbenzothiazole, 5 methylbenzothiazole, 6 methylbenzothiazole, 5 bromobenzothiazole, 6 bromobenzothiazole, 4 pheuylbenzothiazole, 5 phenylbenzothiazole, 4 methoxybenzothiazole, 5 methoxybenzothiazole, 6 methoxybenzothiazole, 5 iodobenzothiazole, 6 iodobenzothiazole, 4 ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenz othiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), those of the naphthothiazole series (e. g. 'a-naphthothiazole, B-naphthothiazole, 5-methoxy-fi-naphthothiazole, 5- ethoxy-p-naphthothiazole, 8-methoxy-m-naphthothiazole, 7-methoxy-ot-naphthothiazole, etc.), those of the thianaphtheno-7,6',4,5-thiazole series (e. g. 4'-methoxythianaphtheno-7',6',4,5-thiazole, etc.), those of the oxazole series (e. g. 4-methyloxazole, S-methyloxazole, 4-pheny1- oxazole, 4,5 diphenyloxazole, 4 ethyloxazole, 4,5- dimethyloxazole, S-phenyloxazole, etc.), those of the benzoxazole series (e. g. benzoxazole, S-chlorobenzoxazole, 5 methylbenzoxazole, 5 phenylbenzoxazole, 6 methylbenzoxazole, 5,6 dimethylbenzoxazole, 4,6- dimethylbenzoaxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, 5 chlorobenzoxazole, 6 methoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),- those of the naphthoxazole series (e. g. a-naphthoxazole, fl-naphthoxazole, etc.), those of the selenazole series (e. g. 4-methylselenazole, 4-phenylselenazole, etc.), those of the benzoselenazole series (e. g. benzoselenazole, 5-chlorobenzoselenazole, 5 methoxybenzoselenazole, 5 1 hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), those of the naphthoselenaz'ole series (e. g. a-

heterocyclic nucleus containing from five to six atoms naphthoselenazole, ,8 naphthoselenazole, etc.), those of the thiazoline series e. g. thiazoline, 4-methylthiazoline, etc.), those of the Z-quinoline series (e. g. quinoline, 3 -methylquinoline, 5 -methylquinoline, 7- methylquinoline, 8 methylquinoline, 6 chloroquineline, 8 chloroquinoline, 6 methoxyquinoline, 6- ethoxyquinoline, 6 hydroxyquinoline, 8 hydroxyquinoline, etc.), those of the 4-quinoline series (e. g. quinoline, 6-methoxyquinoline, 7-methylquinoline, 8- methylquinoline, etc.), those of the l-isoquinoline series (e. g. isoquinoline, 3,4-dihydroisoquinoline, etc.), those of the 3-isoquinoline series (e. g. isoquinoline, etc.), those of the benzimidazole series (e. g. l,3-diethylbenzimidazole, l-ethyl-3phenylbenzimidazole, etc.), those of the 3,3-dialkylindoleniue series (e. g. 3,3-dimethylindol'enine, 3,3,5 trimethylindolenine, 3,3,7 trimethylindolenine, etc.), the pyridine series (e. g. pyridine, S-methylpyridine, etc.), etc., and Q represents the nonmetallic atoms necessary to'complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, such as those selected from the group consisting of those of the thiazolone series, for example: those of the 2,4(3,5)-thiazoledione series, such as 2,4(3,5)-thiazoledione, 3-alkyl- 2,4(3,5) thiazolediones (e. g. 3 ethyl 2,4(3,5)- thiazoledione, etc.), 3-pheny1-2,4(3,5)-thiazoledione, 3- a naphthyl 2,4(3,5) thiazoledione, etc., those of the 2 thio 2,4(3,5) thiazoledione (rhodanine) series, such as 3 alkyl 2 thio 2,4(3,5) thiazolediones 3 (3-alkylrhodanines) (e. g. zoledione (or 3 ethylrhodanine), 3 phenyl 2- thio 2,4(3,5) thiazoledione (3 phenylrhodanine), 3 a -'naphthyl 2 thio 2,4(3,5) thiazoledione (3- a naphthylrhodanine), 3 (1 benzothiazyl) 2 thio- Z,4(3,5) thiazoledione (3 (1 benzothiazyl)rhodanine), etc., those of the 2-alkylmercapto'-4(5)-thiazolone series, such as 2 ethylmer'capto 4(5) thiazolone, etc., those of the thiozolidone series, such as 4-thiazolidbne or its 3=alkyl (e. g. ethyl, etc.), 3-phenyl or 3-a-naphthyl derivatives, those of the 2-alkylphenylamino-4(5)-thiazolone series (e. g. Z-ethylphenylamino- 4(5)-thiazolone, etc.), those of the Z-diphenylamino- 4(5)-thiaz olone series; those of the 5(4)-thiazolone series, such as 2-ethylthio-5(4)-thiazolone, 2-benzylthio- 5(4)-thiazolone, etc., those of the oxazolone series, for example: those of the 2-thio-2,4(3,5)-oxaz0ledione series, such as 3-alkyl-'2thio-2,4(3,5)-0xazolediones (e. g. 3-ethyl'-2-thio-2,4(3,5)-oxazoledione, etc.), those of the 2 imino 2,4(3,5) oxazolone (pseudohydantoin) series, e't'c.; those of the 5('4)'-oxazolone series, such as 2-phenyl- 5(4)-oxazolone,- 2-ethyl5(4)-oxazolone, etc., those of 3-ethyl2-thio-2,4 3,5 -thiathe 5(=4)-isoxazolone series, such as 3-phenyl-5(4) isoxa- 'zolone, etc., those of the imidazolone series, for example: those of the 2 ,4(3,5)-imidazoledione series, such as 2,-4( 3,5)-imidazoledione (hydantoin) or its 3-alkyl ('e.,g. "ethyl, 'etc.), 3-phenyl or 3-tx-naphthyl derivatives as well "as its 1,3'-dialkyl '(e. g. 1,3-diethyl, etc.), l-alkyl-3- phenyl (e. g. l-ethyl-3-phenyl, etc.), 1-alkyl-3-naphthyl (e. g. 1-ethyl-3-u-naphthyl, etc.), 1,3-diphenyl, etc., derivatives, those of the 2-thio-2,4( 3,5 )-imidazoledione series, such as 2-thio-2,4(3,5)-imidazoledione (2-thiohydantoin) or'its 3-alkyl (e. g. 3-ethyl, etc.), 3-phenyl or 3- oz-naphthyl derivatives as well as its 1,3-dialkyl (e. g. 1,-3-diethyl, etc.), l-alkyl-3-phenyl (e. g. l-ethyl-S-phenyl,

etc.), 1-alkyl-3-naphthyl (e. g. 1-ethyl-3-wnaphthyl), 1,3- diphenyl, etc. derivatives, those of the 2-alkylmercapto- -5(4)'-imidazolone series, such as 2-n-propylmercapto 5(4)"-imidazolone; those of the thionaphthenone series, such as 2(1)'-thionaphthenone or 1(2)-thionaphthenone; those of'the pyrazolone "series, such as pyrazolone or its l -alkyl (e. g. methyl, ethyl, etc.), l-phenyl, l-naphthyl (e. g. l-a-naphthyl), 3-alkyl (e. g. methyl, ethyl, etc.), 3-phenyl, 3-naphthyl (3-a-naphthyl), (e. g. 1-methyl-3-phenyl, etc.), 3-alkyl-1-phenyl (e. g. 3- methyl-l-phenyl, etc.), 1,3-dialkyl (e. g. 1,3-dimethyl, etc.), 1,3-diphenyl, etc. derivatives; those of the oxindole series, such as 2,3-dihydro-3-ketoindole, and like fivemembered heterocyclic nuclei; those of the 2,4,6-triketohex'ahydropy'rimidine series, for example, 2,4,6-triketohexahydropyrimidine (barbituric acid), 2 thio 2,4,6 tri- Tke tohexahydropyrimidine (2-thiobarbituric acid) as well as their l-alkyl (e. g. l-ethyl, etc.) or 1,3-dialkyl (1,3- diethyl, etc.) derivatives; those of the 3,4-dihydro-2(1)- quinolone series, such as 3,4-dihydro-2(1)-quinolone (dihydrocarbostyril); those of the 3,4-dihydro-2(1)- quinoxalone series, such as 3,4-dihydro-2(1)-quinoxalone (oxydihydroquinoxaline), etc.; those of the 3-pl1enomorpholone (1,4,3-benzoXazine-3(4)-one or benzo-B- morpholone) series, such as 3-phenomorpholone, etc.; those of the 1,4,2-benzothiazine-3 (4)-one (ketodihydrobenzoparathiazine) series, such as ketodihydrobenzoparathiazine, etc., and like six-membered heterocyclic nuclei.

In accordance with my invention, I provide the dyes represented by Formula I above by condensing together a compound selected from those represented by the following two general formulas:

1-alkyl-3-phenyl wherein R, R1, R2, Z, m, and n each have the values given above, R4 and R5 each represents an alkyl group, such as methyl, ethyl, allyl, carbethoxymethyl, etc., and X represents an acid radical, such as benzenesulfonate, p-toluenesulfonate, etc., with a compound selected from those represented by the following general formula:

III 0R3 ,Q\

urn-(i=6 b=0 wherein R3 and Q each have the values given above.

The condensation of the compounds of Formula II or Ila with those of Formula III can be carried out in the presence of a basic condensing agent, such as the tri-alkylamines (e. g. triethylamine, tri-n-propylamine, tri-nbutylamine, triisobutylamine, etc.), N alkylpiperidines (e. g. N-methylpiperidine, N-ethylpiperidine, etc.), N,N- dialkylanilines (e. g. N,N-dimethylaniline, N,N-diethylaniline, etc.), etc. The 'condensations can advantageously be carried out in the presence of an inert solvent, such as pyridine, lower aliphatic alcohols (e. g. ethanol, n-propanol, "n-butanol, etc.), 1,4-dioxane, etc. Heat accelerates the condensation's, and temperatures varying from room temperature to the reflux temperature of the reaction mixture can be used.

The intermediates of Formula lII above wherein Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the 5 (4)-oxazolone series can be prepared according to the process described in Ilford British Patent 633,736, accepted December 19, 1949. In general, the intermediates of Formula III above can also be prepared by condensing together an ester selected from those represented by the following general formula:

wherein R5 has the values given above with an intermediate selected from those represented by the following general formula:

/'Q\\ Had b -O wherein Q has the values given above, in the presence of a-carboxyli'c anhydride, suchas acetic anhydride, propionic anhydride, etc. The intermediates of Formula 111 above wherein 'Q represents the non-metallic atoms necessary'to complete a heterocyclic nucleus of the 5(4)-thiazolone series have been previously described by Cook et a1. Jour. Chem. Soc. (1949), pages 14354, and in The Chemistry of Penicillin, Princeton University Press (1949), page '803. (For a further description, see the copending application Serial No. 211,566, filed February 17, 1951, in the names of Per Aubert and Edward B. Knott, now U. '8. Patent 2,692,829, issued October 26, 1954, and my copending application Serial No. 224,714, filed May 5, 1951, now U. S. Patent 2,691,581, issued October 12, 1954.)

The intermediates represented by Formula 11 above can advantageously be prepared by heating together a compound selected" from those represented by thetollowing wherein R, R1, R2, R4, m, n, and Z each have the values given'above, with 'an-alkyl salt,'such as those represented by the following general formula:

Example I.-2 [2 (3 carbethoxymethyl 4 x0 2- thiono thiazolidylidene) 2 ethoxyethylidene] 4- [(3 ethyl 2(3) benzothiazolylidene)ethylidenel- 3 methyl 5 thiazolidone wherein R5 and X each have the values given above. Such 2.4 g. of 4-[ (3-ethyl-2(3)-benzothiazolylidene)ethyla process has been previously described in Fry et al. U. S. idenel-Z-ethylthio 5(4) thiazolone methomethylsulfate, P t 2.38 issued November 4 and Brooker 1.5 g. of 3-carbethoxymethyl-5 (u-ethoxyethylidene)- Patent issued November 1943- rhodanine, 10 cc. of ethanol, and 0.9 cc. of tricthylamine intermediates representedby Formula VI above are well were heated on the Steam bath f 5 minutes The dye known as well as the methods of mak1 ng them- F which rapidly separated was collected hot and washed well ample, Kendall U. S. Patent 2,265,908, issued December 9, with ethanol. There was thus obtained 1L0 g. of dye in 1941 g r 2 a i i of makmg dyes of type the form of dark green crystals, having a melting point of resente y 0mm 241 C. after recrystallization from a pyridine-ethanol The intermediates represented by Formula lIa above I d l m b can advantageously be prepared by heating together a F sensltfze a ge atmo S1 ver 6 0m 6 compound selected from those represented by the follow- 1 efnulslon f fnaxlma 645 and 0 and gelatmo ing general f l 25 silver bromiodide emulslon with a maximum at 735 mu.

VH The 3-carbethoXymethyl-5-(oc-ethoxyethylidene)-rhodanine used in the above example was obtained as follows:

(a) 3-carbethoxymethylrhodanine (4.38 g.), ethyl orthoacetate (6.0 cc.), and acetic anhydride (25.0 cc.) I were refluxed for one hour and the solvents removed. There were thus obtained 4.9 g. of residual solid (yield:

wherein R, R1, R2, R4, m, n, and Z each have the values a given above, with an alkyl salt, such as those represented 85% of theory) as sllky bufl needles melting at 105 by Formula VIa above. Alternatively, the intermediates on recrystallizatiml from ligl'oinrepresented by Formula IIa above can be prepared by (b) 3-carboxymethylrhodanine (28.65 g.), ethylorthoheating together a compound Selected from those p acetate (96.0 cc.), and acetic anhydride (300 cc.) were sented by the following general formula: refluxed for one hour and the solvents removed. n-Pro- F 0 panol (50.0 cc.) was added to dissolve the residue and R1 plws 40 the solution chilled. There were thus obtained 15.8 g. R1-I orr='omlf b =d-h i= h-s-'-R.

105 C. on recrystallization from isopropanol. The yield wherein R, R1,'R2, R5, m, n, and Z each have the values was 36% of theory.

Example 2.2 [2 (3 carbethoxymethyl 4 0x0 2- thiono 5 thiazolidylidene) 2 ethoxyethylidenel- 4 [(3 ethyl 2(3) benzoxazolylidene)ethylidene]- 3 methyl 5 thiazolidone 1.65 g. of 4-[(3ethyl-2(3)-benzoxazolylidene)ethylidene]-2-ethylthio-5(4)-thiazolone and 1.0 g. of methyl p-toluenesulfonate were fused at 125130 C. for 60 minutes. There were then added 1.5 g. of 3-carbethoxymethyl-S-(a-ethoxyethylidene)rhodanine, 10 cc. of ethan01, and 0.8 cc. of triethylamine. The mixture was heated on the steam bath for 5 minutes, a thick dye meal sepgiven above, with an alkyl salt, such as those represented by the following general formula:

VIIIa R4-X wherein R; has the values given above. Methodsof making the intermediates represented by Formula 1111 above have been previously described in the copending application of Per Aubert, Roy A., Jefireys, and Edward B. Knott, Serial No. 220,332, filed March 2, 1951, now U. S. Pfltent issued Novembfir 1953- Intermearating rapidly, which was collected and washed with dlatqs representqd by.FrmulaS and .have ethanol. The dye thus obtained weighed 0.5 g. and was previously described in the copending apphcations Serial 211,566, fil d February 17 1951, of Per Aubert and obtained as brilliant green crystals melting at 231 C. Edward B. Knott and Serial No. 203,526, filed December from benzene. It sensitized a gelatino silver chloro- 29, 1950 (now U. S. Patent 2,656,353, issued November bromide emulsion with maxima at 645 700 mu and 20, 1953), of Roy A. Jeffreys and Edward B. Knott.

The following examples will serve to illustrate r a gelatino silver bromiodide emulsion with a maximum at fully the manner whereby I practice my invention.

of product in the form of yellow needles melting at 104- Example 39 -2 [2 (3 carbethoxymethyl 4 0230- 2- thio'no' 5 thiazolidylidene) -'2 ethoxyethylidenel 5- 'l (3 ethyl 2(3) benzothiazolylidene)ethylidene] 3- ethyl 4 thiazolidone e -'-l.75 g. of 5-[(3-ethyl-2(3)-benzothiazolylidene)ethyli- It sensitized a gelatinosilverchlorobromide emulsion with dene]-'3-ethyl-4(5)-thiazolidone and 1.0 g. of methyl max eat 6' 'a p-tolueriesulfonate were fused at 130 C. for one hour. Example [2 ethoxy (2 ethylthio The 'SDlld quaternary salt was broken up, and 1.5 g. of 4 thiazolhlyh-d'ene)gthylidene] 5 [(3 ethyl 2(3) 3'carbethoxyrnethyl-5-(a ethoxyethylidene) rhodanine, benzothiazolylidene)ethylidene] 3 ethyl 4 thiaz0 10.0 cc. of ethanol, and 0.8 cc. of triethylamine were lidone added and heated for 5 minutes on the steam bath. The dye (1.5 g.) was cooled and washed with ethanol. After S g two recrystallizations from benzene-ethanol, it formed (hi-Xmas *8 olive-green leaflets and had a melting point of 197 C. C=G'HOH= =CH- :0 il-soni It sensitized a gelatino silver chlorobromide emulsion with V S maxima at 590 and 700 mu and a gelatino silver bromi- N odide emulsion with maxima at 580 and 700 mu. 5

Example 4.-2 [2 (3 carbethoxymethyl 4 0x0 2- 1 thiono 5 thiazolidylia'ene) 2 ethoxyethylidenel 5- [(3 ethyl 2(3) benzoxazolylidene)ethylidene] 3- ethy'l 4 thiazolidone 1.7 .g. of 5-[(3-ethyl-2(3)-benzoxazolylidene)ethyli- 40 1.0 g. of N-dithiocarbethoxyglycine was treated as in dene] -3-ethyl-4(5)thiazo1idone and 1.0 g. of methyl Example 5. The merocyanine dye of Example 3 (1.75 g.) p-toluenesulfonate were fused at 130 C. for one hour. was quaternized as described in'that example and then The'solid was broken up, and 1.5 g. of 3-carbethoxymixed together withthe residual product treated according methyl-'5 (a-ethoxyethylidene)rhodanine, 10 cc. of ethato Example 5. The mixture was then heated for 5 minnol and 0.8 .cc. of triethylamine were added and heated utes in 10.0 ccoiethanol and 0.8 cc. of triethylamine. The on the steam bath for 5 minutes. The dye (1.2 g.) Was dye (0.9 g.) after an ethanol wash formed glossy, darkcollected' in the form-of'olive green crystals a'nd'it had a green needles melting at 227 C., after tWo recrystallizamelting poiri-t-of2'2-3 C. after two'recrystallizations from tions from benzene-ethanol. It sensitized a gelatino silver benzene; It sensitized a photographic silver chlorochlorobromide emulsion with maxima at 540 and 690 mu bromide emulsion with maxima at 630 and'690 mu and and a photographic silver bromiodide emulsion with a a photographic silver bromiodide emulsion with maxima maximum extending to 710 mu. at 580 and 710 mu.

Example 7.--2- [Z-ethoxy-Z (5 -0x0-2-phenyl-4-oxaz0linylidene)ethylidene] 4 [(3 ethyl 2(3) benzothiazalylidenekthylidene]-3-methyl-5-thiaz0lidone Example 5.- 2 [2 ethoxy 2 (2 ethylthio 5 0x0- 4 thiazolinylia ene)ethylidene] 4 [(3 ethyl 2(3)- benzothiazolylidene)ethylidene] 3 methyl 5 'thiazolidone s i s l o=o--s 00,115 o -s 0=o--s o0,H,'oo

amal awlzl no... to C.CH.OH.4. t.@H t:t ta... N N/ ([JaH s (11; I 7 (1x115 CH| l.0..g.-of N-dithiocarbethoxyglycine, 10.0 cc. of acetic aglydride lt;1nd15t.0 cc. ofhethyl orthoacetate were heated on 1.42 g f h quatemizred memcyanine d f t steam at or one our, at the end of which time the i solvents were removed under reduced pressure. To the 9 of 4-(wgthoxycthylldang)2131mm?- residual,4 ,(a ethoxyethylidene) 2 ethy1thio 5(4) 5 4)-oxazolone, 1.0.0 cc.-of ethanol and 0.5 -cc.-of =tnlone was added 2.4 g..of the .quaternized merocyanine dye ethylamine e at am ath f r 5jIn1'nused in 'Examflle 1, together with 10.0 cc. of ethanol and utes. The dye (0.5 g.) after an ethanol wash formed 058cc. of'trie ylamine. The whole was then heated on 0 the steam' bath for two minutes and the dye which scp- Soft W .needle'sinfeitmg at C aftef Hated rapidly was collected and Washed with vethanol. two recrystallizations fil'OIHLPYTldlHfi-CthQ-HGL It sensi- The dye (0.5 g.) formed soft, green needles melting .at l mofi chlowbromide ,,W h a 251 fter two recrystallizations from benzene-ethanol. maximumatmo mu. v

amazes 9 Example 8.2-[2-(3-cdrbethoxymethyH-oxo-Z-thiom 5 thiazolidylidene) 2 ethoxyethylidene] 5 [(4,5 diphenyl 3 ethyl 2(3) thiazolylldene)- ethylldene] 3 ethyl 4 thiazolidone CCHP 1.5 g. of 5-[(4,5-diphenyl-3-ethyl-2(3)-thiazolylidene) 1.2 g. of 5-[(3-ethyl-2(3)-benzothiazolylidene)ethylethylidene]-3-ethyl-4-thiazolidone and 0.85 g. of methyl idene]-3-phenyl-4-thiazolidone and 0.7 cc. of dimethylp-toluenesulfonate were fused at 130 C. for 45 minutes. sulfate were fused for 5 minutes at 140 C. The solid There were then added 1.0 g. of 3-carbethoxymethyl-5- quaternary salt was then reduced to a powder, 0.9 g. of (a-ethoxyethylidene)rhodanine, 15 cc. of ethanol, and 3 carbethoxymethylq- 5 (a ethoxyethylidene) rho- 0.6 cc. of triethylamine, and the whole refluxed for two anine, 1 .0 cc. of ethanol and 0.6 cc. of triethylamine minutes. The dye (1.2 g.) after an ethanol wash formed were added and the whole heated for 10 minutes on the soft, glossy, green needles melting at 232 C. after two steam bath. The dye (1.2 g.) was washed with ethanol recrystallizations from benzene-ethanol. It sensitized a until the washings were blue and then recrystallized gelatino silver chlorobromide emulsion with maxima at twice from pyridine-ethanol to give olive-green needles 690 and 740 mu and a gelatino silver bromiodide emulmelting at 236 C. It sensitized a gelatino silver chlorosi with a m xi u extending to 800 mu, bromide emulsion with maxima at 620' and 690 mu and Example 9.-2- [2- (3-carbeth0xymethyl-4-oxo-2-thiono-5- v thiazolidylidene) 2 ethoxyethylidene] 4 [(4.5 diphenyl 3 ethyl 2(3) thiazolylidene)ethylidene] 3 methyl 5 thiazolidone 1.5 g. of 4-[(4,5-diphenyl-3-ethyl-2(3)-thiazolylidene)ethylidenel-Z-ethylthio-S(4)-thiazolone and 0.7 g.

a gelatino silver bromiodide emulsion with a maximum at 690 mu.

Example 11.2- [2- (3-carbethoxymethyl-4-ox0-2-thion0- 5 thiazolidylidene) 2 ethoxyethylidene] 5 (3 ethyl 4,5 diphenyl 2(3) thiazolylidene) 3 ethyl 4 thlazolidorre can-4k v 1.3 g. of .'5?(4,5-diphenyl-3-ethyl-2( 3)-thiazolylidene)- of methyl p-toluenesulfonate were fused at 140 C. for

3-ethyl-4-thiazolidone' and 0.6 g. of methyl p-tolueneminutes. There were then added 1.0 g. of 3-carbe- I thoxymethyl-S-(a-ethoxyethylidene)-rhodanine, 15.0 cc. sultonate were fused at 140 C. for 30 minutes. 7 There of ethanol, and 0.6 cc. of triethylamine and the whole were then added 0.9 g. of 3-carbethoxymethyl-5-(arefluxed on the steam bath for 3 minutes. The bronze ethoxyethylidene)rhodanine, 20.0 cc. of ethanol, and crystalline dye (0.8 g.) was boiled together with ethanol 0.5 cc. of triethylamine and the whole refluxed for 15 several times to remove a magenta-colored dye. The minutes. The dye formed mauve Y bronze crystals were then dissolved in hot benzene but als melting at 250 C. after recrystallization from pyrlli d u immediately s green ne dles, After idine-ethanol. It sensitized a gelatino silver chlorobrotwo recrystallizations from pyridine, it formed green mide emulsion with a maximum at '625 mu and a gelatino needles melting at 249 C. with some softening at Silver bromiodide emulsion with a maximum at 620 mu. C. It sensitized a gelatino silver chlorobromide emul- The following examples describe various dyes embraced sion with a maximum at 750 mu. I by Formula I above, the dyes being prepared in sub- Example 10.-2- [2- (3-carbeth0xymethyl-4-oxo-Z-thiono- 5 thiazolidylidene) 2 ethoxyethylidene] 5 [(3 ethyl 2(3) benzothiazolylidene)ethylidene] 3 phenyl 4 thiazolidone I 2,728,766 11 1?. stantially the identical manner illustrated in Examples silver bromiodide emulsion with maxima at,620 and 690 1 to 11. The dyes were obtained by condensing the: mu. a I

Example 1 4.3 calibetlzoxymethyl 2 [2 Q (3 carbethoxy-methyl 4 x0 2 thiono 5 thiazolidyliden'e) 2 ethoxyethylidene] 5 [(3 ethyl 2(3) benzothiazolylidene)ethylidene]-4-thiaz0lidone .CHzCOOCzHt O 2H5 intermediate selected from Formula II or IIa above with This dye was obtained in 61% yield as green threads an intermediate of Formula III ashereinbefore described. having a melting point of 221 C. It sensitized a gelatcondensa'tions were carriedoutin ethanol solution ino silver chlorobromide emulsion with a maximum at usingtriethylamine as the condensing agent. 680 mu and a gelatino silver bromiodide emulsion with a maximum at'690'mu.

Example 12.2-[2-(3-carbethoxymethyl-4-0xo-2-thiono- 5 thiazqlidylidene) 2 ethoxyethylidene] --3 ethyl 5 [(1.3,3 trimethyl 2 1 indolylidene)ethylidenell thiazo lidone P (8H9: ll

\\ O=C-NC:H 0cm, C--N'CH$CO0C2H6 C=CH-CH= =CH 5 (3H1 This dye was obtained as green flakes with a melting 1 Example 15.-3 carbethoxymethyl 2 [2 (3 carbethoxymethyl 4 0x0 2 thiono 5 thiazolidylidene 2 ethoxy ethylidene] 5 [(1 ethyl 2(1) -quinolylidene)ethylidene]-4-thiaz0lidone omoooozm o 0=(:J1YI (502m --NCH=COOO:H5

CHI-CH: 0 CH 0 C\ s s s 2H5 point of 212 C. The yield Was 33%. It sensitized a This dye was obtained as green flakes in yield. It gelatino silver chlorobromide emulsion with maxima at had a melting point of 216 C. and sensitized a gelatino 630and 680 mu and a gelatino silver bromiodide emulsilver chlorobromide emulsion with maxima at 635 and sion with maxima at 600'and 690 mu. 730 mu and a gelatino silver bromiodide emulsion with maxima at 685 and 730 mu.

Example 13.--3 carbethoxymethyl 2 [2 (3 carbethoxymethyl 4 0x0 2 thiono 5 thiazolidylidene) 2-ethoxyethyliderte] 5 [(3 ethyl 2(3.) benzoxazolylid'ene)ethylidene]-4 thiazolidone omooooms o o Ilr a v O=C--- OCiHt IiF-CHaCOOCzHs o=oH- -o11=l: d=on-ls lv 0=s S s N g H This dye .was obtained in the form of violet-brown Example 16'.3 carbethoxymethyl 2 [2 (3 carbezhoxymethyl 4 0x0 2 -'thion 0 5 thiazolidylidene) 2 ethoxyethylidene] 5 [(3 methyl 2(3) thiazolinylia'ene) ethylidene] -4-thiazolidone S CHnC O O C2H5 O O=C--N 00am --N-oH,oo0o,H. H C o=on-on=la =on-r =s H:

N JJH:

threads in 31% yield. It had a melting point of 189 This dye was obtained in 33% yield as green crystals C. and sensitized a gelatino silver chlorobromide emulhaving a melting point of 211 C. It sensitized a gelatino sion with maxima at 610 and 690 mu and a gelatino silver chlorobromide emulsion with maxima at 6-30 and 2,725,700 13 14 690 mu and a gelatino silver'bromiodlde emulsion with a maximum at640 mu.

Example 19.-3 carbethoxymethyl-Z-[2-(3-carbethoxymethyl-4-oxo-2 thiono-5-thiazolidylidene)-2-ethoxyethylidene] 5 [1-(1-ethyl-2(1)-fi-naphth0thiazolylidene)-2-pr0pylidenel-4-thiazolidone This dye was obtained in 23% yield in the form of Example 17.-'-3 carbethoxymethyl 2 [2 (3 carbethoxymethyl 4 0x0 2 thiono 5 thiazolidylidene) 2 ethoxyethylidene] 5 2 [(3 methyl 2(3) thiazolinylidene) -1-pr0pylidene] -4-thiazolidone s cnlcoocefle 0 i on, =CN OCsHs -N-CHgCOOCaH;

This dye was obtained in 30% yield in the form of green flakes having a melting point of 226C. It sengreen crystals having a melting-point of 194-195 C. It sitized a gelatino silver chlorobromide emulsion with a sensitized a gelatino silver chlorobromide emulsion with 30 maximum at 710 mu and a gelatino silver bromiodide a maximum at 650 mu and a gelatino silver bromiodide emulsion with a maximum at 730 mu. emulsion with a maximum at 670 mu.

Ollie-f (JR-ana =CH-l! =s This dye we obtained in 30% yield in the form er Example 18.--3 --carbethoxymethyl 2 [2 (3 earbethoxymethyl 4 0x0 --2 thiono 5 thiazolidylidene) 2 ethoiyethylidene] 5 [(1 ethyl 2(1 B naphthothiazolylidene)ethylidene]4 thiazolidone.

This dye was obtained in 40% yield in the form of green-gold needles having amelting point of 210 C. green powder having "a melting point of 230 C. It It sensitized a gelatino silver chlorobromide emulsion sensitized a gelatino silver chlorobromide emulsion with with a maximum at 770 mu and a gelatino silver bromioa maximum at 690 mu and a gelatino silver bromiodide dide emulsion with a maximum at 780 mu.

emulsion with a maximum at 700 mu.

Example 21.3-carbelh0xymethyl 2 [2-(3-carbeth0xymethyl 4 0x0-2-thi0n0-5-thiazolidylidene)-2-ethoxyethylidenel-S-[O ethyl-2 (3) benzoselenazolylidene) ethylidene]-4-thiazolid0ne tized a gelatino, silver chlorobromide emulsion with a maximum ,at 67011111 and-a gelatino silver bromiodide 16 This dye was obtained in 28% :yield in the form of green crystals and had a melting pointof 212 C. It

vsensitized a gelatino silver chlorobromide emulsion with a maximum at 690 mu and a gelatino silver bromiodide emulsioniwith a maximum :at 6 80 mu. .5 emulsion with a maximum at 700 mu.

' Example 25. 5-[(4,5-diphenyl-3-ethyl-2 (3)-0xaz0lylidene) ethylidene] 3 carbethoxymethyl-Z-[2-(3-carbethoxymethyl-4-0x0-2-thiono 5 thiaz0lidylidene)-Z- ethoxyethylidene]-4-thiaz0lidone CHgCOOCgH; O

Example 22. 3-carbeth0xymethyl-2- [2-(3-carbeth0xymethyl-4-oxo-2-thiono 5 thiazolidylidene) -2-ethoxyethylidene] -5- (1 -ethyl-2 (1 -pyridylidene) ethylidene] 4-thiaz0lid0ne This dye wasobtained in 62% yield in the form, of

zreenthreads-having amelting point of 179 C. It sensi- 30 This dye was obtained in 38% yield in the formof tized a ixelatino silver; chlorobromide emulsion with a maximum at 710 mu anda gelatino silver bromiodide emulsion with maxima at 690 and 740 mu.

green-bronze crystals and had a melting point of 151 C. It sensitized a gelatino silvenchlorobromide emulsion with maxima at 570 and 680 mu'and .a gelatino silver Example 26.t5 .[(4,5 diphenyl 3 ethyl 2(3)- thiazalylidene)ethylidene] --3 carbethoxymethyl 2- [2 (3--- car'beth oxymethyl 4 0x0-- 2 thiono- 5- thiazolidylidene) -'.2 ethoxyethylidene] 4 thiazolibromiodide emulsion with a maximum at 690 mu.

green flakes having .a melting point of 213 C. It sensitized a gelatino silver chlorobromide emulsion with a 60 maximum at 740 mu and a gelatino silver bromiodide emulsion with a maximum at 740 mu.

This dye-was obtained in 37% yield in the form of green needles and had a melting pointof 192 C. It sensitized a gelatino. silver chlorobromide emulsion with Example 24 .5 (1 ,3-diethyl-2 (3 -benzimidazolylidene) ethylidene] 3 carbethoxymethyl-Z-[Z-(3-carbeth0xymethyl-4-oxo-2-thiono 5i thiazolidylidene)-2 ethoxyethylidene] -4-thiaz0lid0ne I 18 This dye was obtained in 10% yield in the form of a maximum at 680 mu and a gelatino silver bromiodide 1 green needles and had a melting point of 212 C. It

emulsion with maxima at 685 and 735 mu.

Example 27. 3-allyl-2-[2-(3-allyl-4-0x0-2-thi0n0-5-thiazolidylidene)-2-ethoxyethylidene] -5-[(3 ethyl 2(3)- benzothiazolylidene)ethyIidene1-4-triazalidane v CHr-0H=0H, 0

O=C--N 00,3. -NCHr-CH=CH: c=cn-cn= 47=OH-(. (a =s This dye was obtained in 39% yield in the form. of 15 sensitized a gelatino silver chlorobromide emulsion with green needles and had a melting point of 227- 'C. 'It a maximum at 685 mu and a gelatino silver bromiodide sensitized a gelatino silver chlorobromide emulsion with I emulsion with maxima at 640 and 680 mu.

Example 30. 3-allyl-2- [2 (3-ally'l -4-ox0'2-thiono-5-thiazolidylidene -2-eth0xyethylidene] 5 1 (3 -ethyl-2 (3 benzothiazolylidene) -2-butylidene] 4-thiazolidone.

JJzHs I This dye was obtained in 45% yield in the form of green needles and had a melting point of 209 C. It

a maximum at 690 mu and a gelatino silver bromiodide emulsion with a maximum at 690 mu.

sensitized a gelatino silver chlorobromide emulsion with a maximum at 690 mu and a gelatino silver bromiodide emulsion with a maximum at 690 mu.

Example 31. [2,-(3 carbethoxymethyl 4 0x0 2- lhiong-S-thiazolidylidene) 2 methoxyethylidene1-3: ethyl-5- [(3-erhyl-2 (3 benzqxazolylidene) ethylidene] 4-thiaz0lid0ne.

This dye Was obtained in 51% yield in the form of Example 29. 3-allyI-2-[2-(3-ethyl-4-oxo-2-thion0 5-, 5 f needles l a melting poiqt of 244 It thiazolidylidene) 2 eth0xyethylidene] 5 [1 (3 ethyl sensitized a gelatino silver chlorobromrde emulsion with 2(3) benzothiazolylidene) Jwmwlidene] thiazom a maximum at 690 mu and a gelatino silver bromiodide Example 32. 3-allyl-2- [2-(3-ullyl-4-oxo-2-thi0rt0 thiazolidylidene) -2-eth0xyethylidene] -5-[1 etlwxy 2- (3 ethyl 2 (3 -benzothiaz0lylidene) ethylidene]-4-thiazolidone This dye was obtained in 12% yield in the form of R2 is an alkoxyl group, can be treated with alkali (e. g. green needles and had a melting point of 200 C. It sodium, potassium, etc., hydroxides) in aqueous solusensitized a gelatino silver chlorobromide emulsion with 15 tion to produce dyes containing a chain-carbonyl group. a maximum at 690 mu and a gelatino silver bromiodide This aspect of my invention is illustrated in the following emulsion with a maximum at 690 mu. examples.

Example 33 2-[2-(3-carbeth0xymethyl 4 0x0 2- thiono-S-thiazolidylidene)-2 methoxyethylidene] 4- [(3 ethyl-2(3) benzothiazolidylidene)ethyliderte1-3- methyl-S-thiazolidone 0=c---s 00H. -N-CH:COOC:H5 G=CH-CH=J3 =CH( 3 :8

N s (.1, (EH:

Example 36.-3-carboxymezhyl-5-(3-ethyl-2(3)-benz0- I thiazolylidene)acetyl-4-hydroxy-2-thionothiazoline This dye was obtained in 31% yield in the form of 0H green needles and had a melting point of 215 C. It s 0 sensitized a gelatino silver chlorobromide emulsion with a a maximum at 730 mu and a gelatino silver bromiodide 35 CF=QH- =3 emulsion with a maximum at 730 mu. S

la-H5 Example 34. 2 [2 (3-carbethoxymethyl 4 0x0 2- thiono 5 thiazolidylidene)-2-methoxyethylidene]-4-. [(3-ethyl-2 (3 )-benz0xaz0lylidene)ethylidene] 3-methyl-S-thiazolidone o=c----s 631 C--- t?t-oH|Oo00,Ha o=on-0n= /G=OHC c=s s (I) 21113 This dye was obtained in 18.% yield in the form of 4.0 g. of 2 -ethylthiobenzothiazole etho-p-toluenesulfogreen needles and had a melting point of 235 C. It 'nate, 2.9 g. of 3-carbethoxymethyl-5-(methoxyethylidene)- sensitized a'gelatinosilverehlorobromide emulsion with rhodanine, 20 cc. of ethanol, and 1.5 cc. of triethylamine a maximum at 700 mu and a gelatino silver bromiodide were refluxed together for 15 minutes and chilled overemulsion with a maximum at 710 mu. night. The precipitated dye weighed 2.8 g. and formed Example 35. 3 allyl -2- [2 (3-allyl-4-0x0-2-thi0n0-5- thiazolidylidene)-2-m'eth0xyethylidene] -5-[1(3 ethyl- 2 (3 -benz0t h-iaz0lylidene -2-butylidene] '4-thiazolidone This dye was obtained'in yield in the form of magenta needles on recrystallization from a benzene green powder and had a melting point of 199 C. It light petroleum mixture. It melted at 127 C.

sensitized a gelatino silver chlorobromide emulsion with p 0.9 g. of the dye obtained above was refluxed in 20 maxima at 620 and 680 mu and a gelatino silver bromcc. of ethanol with a solution of 0.45 g. of potassium iodide emulsion with maxima at 620 and 680 mu. hydroxide in 10 cc. of 'water on the steam bath for It has also been found that the merocarbocyanine dyes minutes. The red solution had then become orange. containing a chain alkoxyl group, such as the dyes of The potassium salt of the desired compound was then Formula II above (prior to quarternization) wherein 75 acidified with dilute hydrochloric acid and the orange 21 ye .6 s as wa hed with ethan l and abta nsd as fin rt. u -c lored. need s tram. ethanol. 1. :nielted t 2 C. an sensitized. a g nuine silver shler b qmid emulsion with a maximum at 510 mu.

Example 37.3 carboxymethyl 5 (I-ethyl2(1)-quinolylidene)acetyl-4-hydroxy-2-thionothiazoline 0 -N-CH:000H GEE-Ll =8 1.35 g. of 3-carbethoxymethyl-S-El-ethoxy-2-(l-ethyl- 2(1)-quinolylidene)ethylidenelrhodanine, 25 cc. of ethanol and 0.7 g. potassium hydroxide in 5 cc. of water were heated on the steam bath for 30 minutes. The orange solution containing the potassium salt of the desired compound was acidified with hydrochloric acid and the dye which slowly crystallized, collected after 24 hours. The dye-weighed 0.6g, representing a yield of 51%. It was obtained as violet needles by dissolving in alcoholic triethylamine and acidifying withacetic acid. It had a melting point of 237 C. and it sensitized a gelatino silver chlorobromide emulsion with a maximum at 520 mu.

Example 38. 3-hllyL-5-(3-ethyL-2 (3) vbenzothiazolylidene) acetyl-4-hydroxy-2-tvhio noth iazoline 1.2 g. of 3-allyl-5-[l-ethOXy-2-(3-ethyl-2(3)-benzoa thiazolylidene)ethylidenelrhodanine was covered with 30 cc. of ethanol and a solution of 0.6 g. of potassium hydroxide in 3 cc. of water added and the whole refluxed for one hour. The bright orange solution containing the potassium salt of the desired compound was acidified with dilute acetic acid. The precipitated dye (64%) formed red needles from ethanol. It had a melting point of 199 C. and it sensitized a, gelatino silver chlorobromide and a gelatino silver bromiodide emulsion with a maximum at 510 mu.

As shown in a number of the above examples, the new dyes of my invention are useful in spectrally sensitizing photographic silver halide emulsions when incorporated therein. The dyes are especially useful for extending the spectral sensitivity of the customarily employed gelatino silver chloride, gelatino silver chlorobromide, gelatino silver bromide, gelatino silver bromiodide, and gelatino silver chlorobromiodide developingout emulsions. V the point of maximum sensitivity of gelatino silver chlorobromide and/ or gelatino silver bromiodide emulsions sensitized with my new dyes is pointed out in connection with the description of the properties of certain of the dyes. To prepare emulsions sensitized with one or more of my new dyes, it is only necessary to disperse the dye or dyes in the emulsions. The methods of incorporating dyes in emulsions are simple and are known to those skilled in the art. In practice, it is convenient to add the dyes to the emulsions in the form of a solution in an appropriate solvent. Pyridine or acetone has proved satisfactory as a solvent for most of my newdyes. The dyes are advantageously incorporated in the finished, washed emulsions and should be uniformly distributed throughout the emulsions. I

The concentration of the dyes in the emulsions can vary widely, e. g. from 5 to 100 mg. per liter of flowable emulsion. The concentration of the dyes will vary according to the type of emulsion and according to the elfect desired. The suitable and most economical con- In several of the foregoing examples,

A quantity of dye is dissolved in pyridine or acetone (or a mixture of acetone and pyridine) and a volume of; this solution, which may be diluted with water, containing from 5 to mg. of dW, is slowly added to about 1000 cc. of gelatinoesilver-halide emulsion, with stirring. Stirring is continued until the dye is thorou h y di p rsed ia'the m ls on- With most of my dyes, from 10 to 20 mg. of dye per liter of gelatino-silver-bromide or bromiodide emulsion (containing about 40 g. of silver halide) sufiices to produce the maximum sensitizing effect. With the finer grain emulsions, somewhat larger concentration of dye may be needed to produce the sensitizing effect.

The above statements are only illustrative, as it will be apparent that the dyes can be incorporated in photographic emulsions by any of the other methods customarily employed in the art, e, g. by bathing a plate or film upon which an emulsion is coated in a solution of the dye in an appropriate solvent. However, bathing methods are ordinarily not to be preferred. Emulsions sensitized with the dyes can be coated on suitable supports, such as glass, cellulose derivative film, resin film or paper in the usual manner.

Photographic silver halide emulsions, such as those listed above, containing the sensitizing dyes of my invention can also contain such addenda as chemical sensitizers (e. g. sulfur sensitizers, such as allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds, such as potassium chloroaurate, auric trichloride, etc. (see U. S. Patents 2,540,085; 2,597,856; and 2,597,915, for example), various palladium compounds (such as palladium chloride (U. 8. 2,540,086), potassium chloropalladate (U. S. 2,598,079), etc.), etc., or mixtures of such sensitizers), antifoggants (e. g. benzotriazole, nitrobenzimidazole, S-nitroindazole, etc. (see Mees-The Theory of the Photographic Process, Macmillan Pub., pg. 460), or mixtures thereof), hardeners (e. g. formaldehyde (U. S. 1,763,533), chrome alum (U. S. 1,763,533), glyoxal (Ger. 538,713), dibromacrolein (Br. 406,750), etc.), color couplers (e. g. such as those described in U. S. Patent 2,423,730, Spence and Carroll U. S. application 771,380, filed August 29, 1947, etc.), or mixtures, of such addend a. Dispersing agents for color couplers, such as substantially water-insoluble, high boiling crystalloidal materials, such as those set forth in U. S. Patents 2,322,027 and 2,304,940, can also be employed in the above-described emulsions.

What I claim as my invention and desire secured by Letters Patent of the United States is:

l. A polymethine dyeselccted from those represented by the following general formula:

wherein R and Rs each represents an alkyl group of the selected from the group consisting of a hydrogen atom,

an alkyl group of the'formula CqHzqfl wherein q represeats a positive integer of from 1 to 3, a phenyl group, a tolyl group, and an alkoxyl group containing from 1 to 2 carbon atoms and at least one of the groups selected from R1 and R2 is a hydrogen atom, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thia-zole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the thiazoline series, those of the thianaphtheno-7',6',4,5-thiazole series, those of the 2-quinoline series, those of the 4-quinoline series, those of the l-isoquinoline series, those of the 3-isoquinoline series, those of the benzimidazole series, those of the 3,3-dialkylindole'nine series, and those of the pyridine series, I and J1 together represent the non-metallic atoms necessary to complete a thiazolidone nucleus, and m and n each represents a positive integer of from 1 to 2, and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing fi'v'e atoms in the heterocyclic ring, three of said atoms being carbon atoms, one of said atoms being a nitrogen atom and the remaining atom being an atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom.

2 A polymethine dye as defined in claim 1 wherein R1 represents a hydrogen atom and m is 2.

3, A p'olymthine dye as defined in claim 1 wherein R2 represents an alkyl group and m is 2.

4. The polymethine dye represented by the following formula:

5. The polymethine dye represented by the following formula:

6. The polymethine dye represented by the following formula;

7. The polymethine dye represented by the following formula:

8, The polymethine dye represented by the following formula:

9. A process for preparing a polyme'thine dye comprising condensing a compound selected from the group consisting of those represented by the following two general formulas:

wherein R, R4, and R5 each represents an alkyl group containing from 1 to 4 carbon atoms, R1 represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CdH2d+1 wherein it represents a positive integer of from 1 to 3, R2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group of the formula C Hz +1 wherein q represents a positive integer of from 1 to 3, a phenyl group, a tolyl group, and an alkoxyl group containing from l to 2 carbon atoms and at least one of the groups selected from R1 and R2 is a hydrogen atom, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the thiazoline series, those of the thianaphtheno-7Q6,4,5-thiazole series, those of the2-quinoline' series, those of the 4-quinoline series, those of the l-isoquinoline series, those of the S-isoquino- ----N-C H10 0 0 01115 line series, those of the benz'imidazole series, those of the 3,3-dia1kylindolenine series, and those of the pyridine 25 series, X represents an acid radical, and m and n each represents a positive integer of from 1 to 2, together with a compoundtselected fromth'ose represented by the following general formula:

0R3 /Q\ onrr l b=o wherein R3 represents an alkyl group and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five atoms in the heterocyclic ring, three of said atoms being carbon atoms, one of said atoms being a nitrogen atom, and the remaining atom being selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.

26 10. A process according to claim 9 wherein the condensation is carried out in the presence of a basic condensing agent.

11. A process according to claim 10 wherein the basic condensing agent is triethylamine.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A POLYMETHINE DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 